Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
  • C08G65/32—Polymers modified by chemical after-treatment
  • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
  • C08G65/334—Polymers modified by chemical after-treatment with organic compounds containing sulfur
  • C08G65/3344—Polymers modified by chemical after-treatment with organic compounds containing sulfur containing oxygen in addition to sulfur
  • C08G65/3346—Polymers modified by chemical after-treatment with organic compounds containing sulfur containing oxygen in addition to sulfur having sulfur bound to carbon and oxygen
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
  • C07C41/01—Preparation of ethers
  • C07C41/16—Preparation of ethers by reaction of esters of mineral or organic acids with hydroxy or O-metal groups

Definitions

• the present invention relates to an improved pro­cess for the preparation of etherified polyoxyalkylene derivatives by reacting the corresponding free hydroxy com­pound with a dialkyl sulfate in the presence of an aqueous solution of an alkali metal hydroxide. More specifically, the present invention is directed to an improved method for preparing methyl ethers of polyether polyol employing dimethylsulfate as a methylating agent.
• polyoxyalkylene compounds having one or more terminal hydroxyl groups can be etherified by first converting the free hydroxy compound with an alkali metal, an alcoholate, a hydride or a hydroxide of an alkali metal into the corresponding alkali metal alcoholate and then further reacting the alcoholate with an alkylating agent, such as, dialkyl sulfate or an alkyl halide.
• an alkylating agent such as, dialkyl sulfate or an alkyl halide.
• German Patent Application 2 800 710 discloses a process for the preparation of etherified polyoxyalkylene compounds in which the free hydroxy compound is treated with an organic halide, such as butyl chloride in the presence of an aqueous solution of sodium hydroxide or potassium hydrox­ide whose initial concentration is of sodium or potassium hydroxide is not less than 30 percent by weight.
• the pro­cess of the German disclosure is carried out at a tempera­ture of from about 80-100°C.
• European Patent 302487 discloses a process for the preparation of etherified polyoxyalkylene derivatives by reacting the corresponding free hydroxy compound with a dialkyl sulfate in the presence of an aqueous solution of an alkali metal hydroxide.
• the reference discribes a two-step process where it is essential to add reactants in a two-step process to form the etherified polyoxyalkylene derivative.
• the present invention relates to a single step process wherein improved yields and substantial savings in time and costs are realized.
• East German Patent 244 549 discloses a process for etherification of oligoglycol monochlorides which is characterized by the fact that the oligoglycol chlorides are reacted with dialkyl sulfates in the presence of an inor­ ganic base at temperatures usual for alkylation reactions.
• the ethers produced are useful for pharmaceutically active substance, surfactants and pesticides.
• Hay, U.S. Patent No. 3,402,144 discloses a pro­cess to metalate polyphenylene ethers with alkali metal alkyls or aryls to give activated alkali metal-containing polymers. These metalated polymers readily react with chemical reagents to produce modified polymers, and also react with anionically polymerizable monomers to produce graft copolymers.
• Leverett U.S. Patent 3,393,179, discloses a pro­cess for the preparation of a high molecular weight polyoxy­methylene alkyl ether which consists of contacting the unetherified polymer with a combination of dimethyl or diethyl sulfate and an orthoester in a process which does not require the addition of a base or acid to catalyze the reaction.
• the reaction temperature is in the range of 100°C to 180°C and preferably is carried out in an inert hydro­carbon medium.
• the present invention relates to an improved pro­cess for the preparation of methyl ethers of polyethers employing dimethyl sulfate as the methylating agent.
• the process is carried out under ambient temperatures of 35°C or less and involves adding all the sodium hydroxide metalating agent at the beginning of the reaction and gradually adding dimethyl sulfate (DMS) over a period of time to give optimal capping of the polyethers.
• DMS dimethyl sulfate
• the present invention is operated at low temperatures, whereas the processes of the prior art operate at elevated temperatures. It was unexpected to find that keeping the reaction temperature below 35°C along with adding all of the NaOH prior to adding the DMS, results in significant improvements in capping efficiency.
• the present invention is concerned with an improved method of preparing alkyl, aryl, or alkaryl ethers of polyethers employing dialkyl, diaryl, or dialkaryl sulfate as the methylating agent.
• the present invention is concerned with the preparation of polyoxyalkylene derivatives of the formula: wherein R1 and R4 are identical or different and are each independently a C1-C20 alkyl, C3-C5 alkenyl, C6-C20 aryl, C6-C20 alkyl aryl, C6-C20 cycloalkyl, and mixture thereof, R2 and R3 are identical or different and independently of each other are each hydrogen, methyl or ethyl, and mixtures thereof, and m, m′ and n are identical or different and are each greater than or equal to 0, with the proviso that the sum of m + m′ + n is from 3 to 300.
• the polyoxyalkylene derivative of formula I is prepared by reacting a polyoxyalkylene compound of the following formula: wherein R5 is hydrogen, C1-C20-alkyl, C3-C5-alkenyl, C6-C20 aryl, C6-C20 alkyl aryl, C6-C20 cycloalkyl groups, and mix­tures thereof, and R2, R3, m, m′ and n each have the above defined meanings.
• the polyoxyalkylene compound of formula II is reacted with a dialkyl, diaryl, dialkylaryl, or cyclo­alkyl sulfate of the following formula: (R4O)2SO2 (III) where R4 has the above meaning.
• the polyoxyalkylene com­pound of Formula II is reacted with the sulfate of Formula III in the presence of an aqueous solution of an alkali metal hydroxide at a reaction temperature of from about 20 to 35°C, and not less than one mole of alkali metal hydroxide is used per mole equivalent of organic hydroxyl groups.
• R1, R4 and R5 may be selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, iso­butyl, or sec-butyl.
• R1 and R5 can further be selected from the group consisting of pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, 2-methyl-pentyl, heptyl, octyl, 2-ethylhexyl, isooctyl, nonyl, isononyl, decyl, iso­decyl, undecyl, dodecyl, tridecyl, 3,5,5,7-tetramethylnonyl, isotridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecy
• R5 is hydrogen or a C8-C16 alkyl group.
• Other preferred polyoxyalkylene derivatives of Formula II are those in which the sum of m, m′ and n is from 3 to 300 or preferably from 5 to 100.
• the preferred alkylating agent is a dialkyl sul­fate of Formula III where R4 is ethyl or most preferably, methyl. If polyoxyalkylene derivatives of Formula II where R5 is hydrogen are used as the starting materials, dietheri­fication occurs. In the case of dietherification, etheri­fied polyoxyalkylene derivatives of Formula I where R1 is identical to R4 are obtained.
• alkali metal hydroxides which are suitable for use in the present invention may be selected from the group consisting of lithium hydroxide, potassium hydroxide, sodium hydroxide and mixtures thereof. In the most preferred embodiment, sodium hydroxide aqueous solution is prefer strictlyred.
• This process is useful in capping oxyalkylated block copolymers and heteric copolymers, oxyalkylated alcohols, oxyalkylated alkylphenols including other initiators such as amines, polyamines, glycerine, trimethylolpropane, pentaerythritol, sugars and related polyhydroxy aromatics, phenolic resins and any other suitable active hydrogen baring compound whose oxyalkylates are not hydrolizable under the conditions described herein, polyethylene glycols, polypropylene glycols, and alcohols.
• the reaction scheme of the present invention may be depicted as follows:
• methyl ethers of polyether polyols are used as low-foam, antifoaming, chlorine-stable surfactants for formulations for cleaning hard surfaces such as particu­larly bottles and cutlery by mechanical cleaning methods (bottle-washing equipment and dishwashers), but also metal surfaces.
• These cleansing operations require surfactants which foam as little as possible, suppress any foam caused by impurities entrained with the materials to be cleaned, and are stable in alkaline solution and in formulations con­taining hypochlorite.
• DIMETHYL-CAPPED POLYOL SYNTHETIC PROCEDURE "A" (PRIOR ART EXAMPLE) CHARGES: 1) EOxPOyEOx copolymer, ca. 13 wt. % EO, molecular weight ca.
• the mixture is then reacted out for a minimum of 80 minutes, followed by the addition of the water (7). Stirring is continued for a minimum of 30 minutes. Stirring is terminated and the contents of the vessel are transferred to a separatory funnel. The mixture is allowed to stand undisturbed. Within seconds, the water and organic layers begin to separate, and the water layer is drained. Approximately thirty to sixty minutes are allowed for the separation.
• the crude product is transferred to a round-bottom flask and is treated with magnesium silicate adsorbent (ca. 3% by weight), followed by stripping at ⁇ 1 mm Hg and 105 C for 2.5 hours. The stripped material is then filtered through #4 Whatman paper to yield the final product. The percent capping of the product is determined from its hydroxyl number.
• An alternative treatment of the crude product is the neutralization of the residual NaOH with phosphoric acid (the charge being determined via titration of the alkali in the crude product), followed by stripping in like manner, with optional filtration.
• DIMETHYL-CAPPED POLYOL SYNTHETIC PROCEDURE "B" (PRESENT INVENTION) CHARGES: 1. EOxPOyEOx copolymer, ca.
• the mixture is then allowed to react out for about 2.5 hours, followed by the addition of the water (4). Stirring is continued for a minimum of 30 minutes. Stirring is termin­ated and the contents of the vessel are transferred to a separatory funnel. The mixture is allowed to stand undis­turbed. Within seconds, the water and organic layers begin to separate, and the water layer is drained. Approximately thirty to sixty minutes are allowed for the separation.
• the crude product is transferred to a round-bottom flask and is treated with magnesium silicate adsorbent (ca. 3% by weight), followed by stripping at ⁇ 1 mm Hg and 105° C for 2.5 hours.
• the stripped material is then filtered through f4 Whatman paper to yield the final product.
• the percent capping of the product is determined from its hydroxyl number.
• An alternative treatment of the crude product is the neutraliza­tion of the residual NaOH with phosphoric acid or some other mineral or organic acid the charge being determined via titration of the alkali in the crude product), followed by stripping in like manner, with optional filtration.
• Examples 1 and 2 are preparations employing the prior art Procedure "A”, without and with auxiliary cooling, respectively.
• Examples 3 and 4 employ the present invention Procedure “B”, without and with cooling, respectively.
• Examples 5, 6, and 7 follow modifications of Procedure B ⁇ ; S and 6 employ a rapid DMS addition with and without cooling, respectively, while 7 uses 20 % less dimethyl sulfate (with cooling).
• Example 7 shows that, when all of the sodium hydroxide is added to the polyether at the beginning, reduced levels of DMS still provide for very high capping effi­ciency.
• Example 8 can be considered to be a modification of Procedure "A” employing shorter caustic and DMS addition times.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Detergent Compositions (AREA)
• Polyethers (AREA)

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• 1989
  • 1989-11-08 US US07/433,133 patent/US4994626A/en not_active Expired - Lifetime
• 1990
  • 1990-10-30 EP EP19900120768 patent/EP0427088A3/en not_active Withdrawn
  • 1990-11-06 JP JP2299094A patent/JPH03173844A/ja active Pending
  • 1990-11-07 CA CA002029509A patent/CA2029509C/fr not_active Expired - Lifetime

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